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16O ratios of minerals of possible mantle or lower crustal origin
EARTH AND PLANETARY SCIENCE LETTERS 9 (1970) 232-239. NORTH-HOLLAND PUBLISHING COMPANY
I)~H A N D 1 8 0 / 1 6 0
RATIOS OF MINERALS OR LOWER CRUSTAL
OF POSSIBLE MANTLE
ORIGIN*
Simon M.F SHEPPARD** and Samuel EPSTEIN Dtvtslon of Geologtcal Sctences, Cahfornta Institute of Technology, Pasadena, California 91109 Received 3 June 1970 Revised version recewed 7 June 1970
D/H and 180/160 analyses are reported for 16 phlogopltes from 11 alkahc intrusions m the USA, Canada, South Africa, India and Austraha The D/H ratio of unaltered phlogoplte of possible mantle or lower crustal origin 1s-58 + 18 per rod, with no slgmficant vanatlon through space or time over the last 1140 my Phlogopltes and calcites from Bachelor Lake, Quebec, and hornblendes and a serpentine from St Paul's Rocks have undergone some isotopic exchange, possibly with ocean water at the latter locahty The D/H ratio m "juvende water" is estimated to be -48 + 20 per mfl
1. Introduction We have investigated the vanabihty of the D/H ratxo o f hydrous minerals o f possible mantle or lower crustal origin and attempt to set hm~ts on the D/H ratio o f "juvende water . . . . Juvenile water" refers here to that water which has never been part of the meteoric cycle. To determine the probable orxgm of volatfles m the earth's crust it ~s essentml that we can characterlze the various possible source materials. Recently the combined analyses for D/H and 180/160 m waters or hydrous minerals have been apphed with success to distinguish the connate, meteoric or primary magmatlc ongm o f a variety of crustal waters such as saline formation waters [ 1 ], geothermal waters [2], hydrothermal solutions [3,4] and the mflux o f meteoric waters into shallow igneous intrusions [ 5 - 7 ] . The 5180 content o f deep-seated water in lugh temperature isotopic equlhbrmm with slhcates ts basically that o f the rock. The composition o f this wa* Pubhcatlons of the Dlvaslon of Geological Sciences, Callforma Institute of Technology, Pasadena, Cahforma, Contrlbutaon No 1725. ** Now at Scottish Research Reactor Centre, East Kflbnde, Scotland.
ter is inferred to be 7 to 8 per mil [8] Since most rocks of deep-seated ongm c6ntam only a few per cent o f hydrogen, their D/H ratio is more diagnostic of "juvenile water". Thus hydrogen extracted from hydrous minerals o f such rocks is characteristic o f the OH or H 2 0 in the lower crust or upper mantle, and any interaction wlth meteoric ground waters should be lsotoplcally recogmzable The D/H ratio o f deepseated hydrogen is presently less satisfactorily defined because of b o t h the hmlted data available on statable samples [ 9 - 1 2 ] and incomplete experimental mineral-water fractlonatlon data [ 13 ]
2. Isotopic analyses and results Hydrogen and oxygen were quantitatively extracted after removal o f all absorbed water at temperatures o f 120 to 200°C from the pure mineral separates and the D/H and 180/160 ratios determined mass spectrometncally [ 1 4 - 1 6 ] Both D/H and 180/160 ratios are reported relatwe to standard mean ocean water (SMOW) m per mil umts. The overall analytical precision is + 0 . 1 - 0 . 2 per mil for 180/160, -+ 2 - 3 per mtl for D/H, and about + 0.05 per cent for H 2 0 content. Sixteen phlogopltes, occurring largely as fresh phe-
D/H AND tSO/t~O RATIOS
233
Table 1 Analytical results - phlogopltes. Sample No
Description
5D (%o)
51 a O ( %o )
Wt% H20
Age (my)
Ref.
Rose dome, Kansas 703B
Mica pendotlte
- 6 5 -+ 2 (2)
72
3 00
90*
[17]
- 5 0 - 3 (2) -63
6 0 +- 0 0 (2) 6.5
3 39 3.08
390**
[17]
- 5 6 + 4 (2)
6 0 + 0 2 (2)
2 97
267**
[17]
-60
7.3
4 96
269**
[17]
- 5 7 + 3 (3)
6 2 -+0 1 (2)
3.82
136"**
[17]
-75 + 1 (2)
6 9 +- 0 1 (2)
4.57
-48
68
4 44
146"**
[17]
- 43 + 3 (4) - 8 3 + 3 (2)
6 4 + 0.0 (2) 8 2 + 0.0 (2)
3.80 5 55
Klmberhte Klmberhte
-92 -92
7 9 + 0 0 (2) 5 9 + 0.1 (2)
3 69 3 64
1100"
[18,19]
Kmaberhte
- 7 0 + 2 (2)
66
3 37
1140"
[22,23]
-60
6.2 -+ 0 1 (2)
4.70
L. Cret
6 3 + 0.1 (2)
3 60
L. Cret
2 67
170"
Avon, Missouri 192B 194B
Ktmberhte Klmberhte
Roslclare, Ilhnols 189B
Kmabedlte
Elhott County, Kentucky 555B(b)
Klmberhte
Portland Pomt, New York 190B(c) 190B(d)
Klmberhte, xenocryst, excess Ar Fine-grained matrix with 190B(c)
Manhelm, New York 193B(a) 193B(b) 193B(c)
Klmberhte, xenocryst, excess Ar Fme-gramed matrix with 193B(a) and (b)
Bachelor Lake, Quebec P2zl P3 Panna, Indm GA 772
Phoenix Pipe, Kimberley, South Afnca K7
Kunberhte xenocryst
Dutoltspan Pipe, Ktmberley, South Africa Kma 8
Mica peridotlte xenocryst
- 5 3 + 4 (3)
Delegate, N S.W., Austraha GA 303
Basic pipe with Inclusions, excess At
-70
(8 8 + 0 3 (2)) 1
[20,21]
* K-Ar age only ** K-At and Rb-Sr ages concordant *** Rb-Sr age only, excess argon
1 There was sufficient coarse grained mica sample to do only a D/H analysis The taO/160 analyses were done on the associated finer grained mica. Our experience wtth the Manhetm sample suggests that the relationship between the D/H and 1aO/160 ratios of these two different separates may not be meaningful
Sunon M.F. SHEPPARD and Samuel EPSTEIN
234
Table 2 Analytacal results - hornblende, serpentine, calcite. Sample No.
Description
8D (%o)
61 s O (%0)
813 C (%0 PDB)
Ref.
St. Paul's Rocks SE-13 SE-13 SE-30 NE-4
Hornblende mylomte, whole rock Hornblende concentrate Hornblende mylomte, hornblende concentrate Serpentine from partially serpentmlzed perldotlte
-33
66
-36 - 4 0 +4 (2)
5 4 +0 3 (2) 5 4 +0.1 (2)
- 3 9 + 2 (2)
63
[24]
Bachelor Lake, Quebec l P2zl P3 P5d
Ktmberhte, calcite Klmberhte, calcite Ktmberhte, calcite
-6.1 -4 5 -5 6
9.5 10.1 104
[18,191
1 Twenty carbonates average STSr/a6Sr = 0 7040 + 0 0005, Sr = 3950 + 1500 ppm [29] nocrysts and xenocrysts, from 10 different alkahc Intrusions (klmberhtes and mica peridoutes) and one mafic breccia pipe were isotoplcally analyzed from locahtles m eastern and central North America, South Africa, Indm and Austraha, and two hornblendes and a serpentine from the St. Paul's Rocks All but the two South African phlogopltes were studied b y Zartman et al. [17] (eastern and central USA), Watson [18,19] (Quebec), Lovering and Rlchards [20], Lovermg and White [21] (Austraha), Crawford [22], Lovermg [23] (Indm) and Melson et al. [24] (St. Paul's Rocks), prowdmg data regarding their age, composition, petrography, etc The xsotop~c data, water content and summary descrlpt~ons are gwen m tables 1 and 2 Partml chemical analyses o f the two South African and Bachelor Lake, Quebec phlogopltes are given m table 3.
Our samples cover a variety of locations, range m age from Precambrlan (1140 my) to Cretaceous, have variations m K 2 0 and H 2 0 contents, and some contain excess argon Although there are b o t h natural and experimental data suggesting that primary phlogoplte Is or could be present m the upper mantle [ 2 5 - 2 7 ] , the depths o f crystalhzat~on o f our phlogopltes are unknown
3. Discussion
3 1. Phlogopttes The Isotopic data, tables 1 and 2, are compared m fig. 1 with sample location and age, and m fig. 2 with previous isotopic data for b~ot~tes from carbonatltes, other ultramafics, and plutonic granites and grano-
Table 3 Partial chemical analyses of phlogopltes (m weight per cent) *
K7 Kun 8 P2zl 190B(d)
Sample
K20
Phoemx, S Africa Dutoltspan, S Africa Bachelor Lake, Quebec Portland Point, New York
6.45 9 36 8 25 7.39**
* Analyst K Hoops using atomic absorption spectrophotometry ** Compare with 7 32 by Zartman et al. [17] *** Total tron as FeO
FeO** *
MgO
4 81 8.22 9 06 6.09
26 7 21 1 21 1 24.9
D/H AND lSO/160 RATIOS
-80
-400
ALKALIC INTRUSIONS Panna, India Bachelor Lake Avon
,age I (m;y.) 1"140 f fO0 390 269 Elliott Co Ros,clare =°67 Manhelm Y46 Portland Point ¢36 Rose Dome 90 L Cret S. Africa
I
I
-60 I
-40
I
I
The 180/160 ratios of the klmberlitic and pendotatm phlogopites are similar to values for whole rock ultramafic and mafic rocks (fig. 2) but tend to be slightly enriched in 180 by up to 1 to 2 per mfl relative to carbonatltlC micas [28] No simple correlation between 180/160 and D/H is observed. The water contents of most of our micas are very comparable to other igneous blotltes [e g 16,28] However, the xenocrysnc micas from Elhott County and the Phoenix pipe have OH-contents larger than the theoretical amount of OH in phlogoplte (4.3 wt per cent H 2 0 ) Both samples are associated with minor hydrous alteration products as detected by X-ray analyses, and have low K 2 0 contents (Elhott C o , 5 3 wt %, Phoenix, 6 5 w.t %) [table 2 in 17, table 3]. These data are not used to set limits on the D/H value of deep-seated water Excluding the Bachelor Lake (see below), EUlott Co. and Phoenix micas there is a tendency for the more D-rich xenocrysts to have a higher water content (fig 3) The four carbonatmc micas also show this tendency There is no relationship between K 2 0 and H 2 0 contents. Isotopic evidence for alteration possibly exists for the Bachelor Lake and the fine-grained matrix micas associated with the coarse xenocrystlc phlogopltes from Portland Point and Manhelm, New York Thus, our samples in general appear to be suitable for studylng "juvemle water" Considering the variety of field associations and tectonic environments represented by the alkahc, ul-
-20
I
I
I I I
H I I I
I
BASIC PIPE Delegate
170
I
ST. PAUL'S ROCKS ¢
SE-43 (hbl) S E - 3 0 (hbl) NE - 4 (serp)
¢
X I -400
I
I -80
I
I
I
I
-60
I
-40
-20
aD(%.) Fig. 1. Comparison of the D/H ratios of pheno- and xenocrystic phlogopltes from alkahc and basic intrusions with thetr locatmn and age. Included are data for hornblendes and serpentine from St Paul's Rocks dlontes. The range of the D/H ratios for pheno- and xenocrystlc phlogopltes is small, especially relative to that for hiotites from gramtlc intrusive rocks (fig 2) No age effect is observed. Five analyzed phlogopites from carbonatltes and a pyroxenlte [9] overlap the D-range observed here. 8D is independent of the excess argon content I
Maflc & Ultramaflc
I
I
235
I
I I I I: :l;,:::l:
BLft~
I
I
:
I-4-1
St Paul's Rocks Carbonahtes
II
Ultramaflcs [9,40]
II
.^,18. | v
,
l
to -455 I -400
I
iii w
I
I
I
II II .,
Maflcs [5AL42] Plutonm Gramtes & Granodmr#es [6,7,9A51
I
eL,,"m'H l~L
v
,
I I
I -80
I
I -60
8D (%.)
I
I -40
I 4
I 6
I
I 8
8 040 (%.)
Fig. 2 Comparison of the D/H and 180/160 ratios of minerals analyzed m this study wtth D/H data for phlogopltes or blotites from carbonatltes [9,28], ultramaflcs [9], plutomc gramtes and granodlontes [6,7,9,15], and for whole rock Hawaiian basalts [ll,12],and 18 O/ 'I-6 Odataforwholerocksfromultramaflcs[10],andmaflcs[5] Where a large number of 1 8 O/ 1 6 Odataare avalhble the isotopic range, mean and number of analyses are indicated BL = Bachelor Lake
236
Stmon M F SHEPPARD and Samuel EPSTEIN
iI
I I I I I I I 1
I I t I PHLOGOPITES
Manhelmo~
-. ~
004
4
"-:~ B a c h e l o r
~.~' L a k e
2 -t00
X
I
I -90
I
•
"-~ X ~*
I -80
X
I
I -70
I
-""*
"
Xo •
-
"'~ "-..
•
5~--
-
X Corbonahtes
""" Ec° P o r t l a n d ,.~ " - - . . . = Ph Point v~........ "-.
~
_
Ultramahcs 0 Matrix
•
-
•
I -60
with an Isotopic reservoir m which the xenocrysts were formed or possible exchange with local meteoric waters In either case xt ~s slgmficant that these relatwely large ~D differences are preserved in a single sample
-
f
I -50
f
I -40
~D (%0) Fig 3 Plot of 6D values for phlogopttes vs their water contents Data for the carbonatlt~c phlogopltes are taken from Taylor and Epstem [ 9 ] , and Taylor et al [28] Dashed hnes are drawn between coarse xenocrystlc phlogoplte and associated fine-grained matrix phlogoptte Ec = Elhott County, Ph = Phoemx pipe
tramafxc, carbonatltlc and basic micas, the range of 6D is quite restricted Although our rocks are not chemically representatwe of the mantle, we assume that our D/H ratios are broadly representatwe since isotopic fractlonatlons among different mineral phases are probably near zero at mantle temperatures However, small heterogeneltxes m D/H ratio could exist as a result of compositional variations m minerals and to the degassmghlstory Evaluation of the small varmtxons in both D/H and 180/160 of the micas must await further data
3 2. Matrtx phlogopttes The coarser grained xenocrystlc Manhelm and Portland Point phlogopltes are assocmted with finegrained matrix phlogopltes of either xenocrystlc or authlgemc ongm In bott. samples the water contents, D/H and 180/160 ratios of the matrix are &stmctly different from their assocmted coarser material (fig. 3), the 180/160 and water contents are higher and D/H ratxo Is lower Excess argon is not present in the matrix micas The ~sotoplc data indicate that the matrLX and associated coarse materxal were not formed under the same con&tlons The observed hydrogen and oxygen isotope differences are consistent with a lower temperature of exchange for the matrix mica
3.3. Bach elor Lake The Bachelor Lake phlogopltes are 20 per md or more lighter m D than any of our other samples and thus appear anomalous (fig. 2) Calcites coexisting with these phlogopltes (table 2) have 8180 values slgmficantly different from primary igneous carbonatlte values (6.0 to 8 5 per md) which represent high temperature equdlbratlon with slhcates [28] Such hydrogen and oxygen isotope compositions could result from the following (1) isotopic exchange with local ground waters, and (2) exchange with the hydrogen and oxygen containing reservoir to lower temperatures The slmdarltles between the 13C/12C ratios of the calcites and primary Igneous carbonatltlC calcites ( - 5 to - 8 per mtl,[28]) suggests that ff hydro° thermal exchange processes continued to submagrnao tic temperatures then the 13C/12C ratio of the exchange system was buffered by the calcites The carbon and oxygen isotope data dxscount weathering, or exchange with ground waters at earth-surface temperatures They do not necessardy exclude exchange at higher temperatures, m agreement with the low value for the 87Sr/86Sr ratio and the relatwely high Sr content of the calcites (table 2) [29]. All the isotopic data are consistent with late alteratlon, suggesting that exchange processes too&fled the once normal klmberhtlc or carbonatitlc isotopic ratios Therefore the D/H rattos of the Bachelor Lake m~cas are not used here to set ltmlts on mantle or lower crustal D/H values. 3.4. St Paul's R o c k The St. Paul's Rocks on the mid-Atlantic Ridge have been considered a htgh-temperature mantlederwed intrusion [24,30] Two hornblende concentrates and total rock were lsotoplcaUy analyzed from the brown alkah-nch hornblende mylomtes of the Southeast Islet (table 2) Smce hornblende is overwhelmlngly the dominant hydrous mineral present, the measured D/H ratios m these samples were not slgmficantly different The 180/160 ratios, which are more sensitive to the presence of Impurities, are
D/H AND 180/160 RATIOS different by about 1 per rml. We note that both primary and recrystallized hornblende, which could not be physically separated, coexist m each sample [24] The D/H ratios of the St. Paul's Rocks hornblendes are slightly enriched in deutermm relative to the igneous phlogopltes (fig. 2). The hydrogen isotope properties of biotite and hornblende are essentially similar as there IS no appreciable fractlonation of D between coexisting igneous biotite and hornblende [ 15]. The implied hydrogen ISOtope change could be lndicatwe of high-temperature exchange with a D-rich reservoir such as ocean water or possibly be a result of differences In chemistry of these amphiboles. These hornblendes have 180/160 ratios strndar to many other ultramafic and mafic hornblendes [5] The apparent lack of an accompanying oxygen ISOtope change could be a result of a very small ocean-water rock ratio so that the slhcate oxygen essentially controlled the 180/160 raho of the system Exchange may have occurred wlth recrystallizatlon during and after mylomtizatlon Chlorine-rich and hydrous phases are Important In the recrystallized assemblages [24] Further discussion must await the resolution of any ISOtopic differences between the primary and recrystallized hornblende The serpentine from the Northeast Islet is enriched in D relative to serpentmlte from the mld-Atlantlc Ridge and from the mohole test at Mayaguez, Puerto Rico [31 ] Exchange with oceanic water may be indicated. Thus, we exclude the D/H ratio of the St. Paul's Rocks hornblende as a candidate for the D/H ratio of "primary OH"
3 5. "Juventle water" We assign the D/H ratio of deep-seated phlogopltes, which have not undergone exchange at low temperatures, to be - 5 8 -+ 18 per mil. The isotopic composition of "juvenile water" depends upon the fractlonation factor between mica or amphibole and water PrehmInary experimentally determmed equilibrium ISOtOpic data by Suzuoki and Epstein [13] and an estimate by Sheppard et al [table 4 In 3] suggest that the hydrogen isotope fractIonatlon between phlogopite and water is on the order o f - 1 0 per mI1 at high temperatures (~ 700°C), indicating a 6D value of - 4 8 +- 20 per md In "]uvende water". We note that .~rnason and SlgurgeIrsson [32] mea-
237
sured 6D = - 5 5 3 -+ 0 5 per mil for the total hydrogen (water plus hydrogen gas) contained an the uncorttaminated volcanic gases over a 2.5 year period from Surtsey, Iceland These data combined with average 6D values for whole rock Hawanan basalts (-75%o) [11,12] set an approximate range of - 5 5 to - 7 5 per mll on the 6D value for total hydrogen in basalts. This range must be considered as very approximate since D/H ratios in Hawauan basalts are variable [ 12], and fractlonatlon of D caused by processes within the magma and associated,with the release of volatdes during eruption are lncomlSletely known. It is relevant to point out that If "juvenile water" in the lower crust or mantle is entirely in the form of "OH" then the isotopic composition could be that of OH reported here On the other hand, the attempt to define a ngld value for the D/H ratio of "juvenile water" may not be legitimate for two reasons (1) the very processes of degasslng of the earth's crust and mantle may affect an ISOtOpicchange m the "juvenile water", and (2) the D/H ratio of material refluxed back into the mantle from the crust may not be constant with either time or place It would be most Interesting to investigate a possible time effect on the D/H ratio of deep-seated water Our samples represent a rather narrow range In time (1140 my to present) We are cognizant of the prelmalnary nature of our assignment of the D/H values.
4. Conclusions 1 The D/H ratio of phlogoplte (or hornblende) of possible mantle or lower crustal origin is - 5 8 +- 18 per mll, with little variation through space or time over the last 1140 my. 2 The present estmaate for the D/H ratio in "juvende water" IS - 4 8 + 20 per mfl 3 Samples from Bachelor Lake, Quebec either have exchanged with local ground water or more probably have undergone oxygen and hydrogen isotope hydrothermal exchange processes without affecting the "primary" carbonatltlC value for 13C/12C ratio In the associated calcite. 4. To account for the higher D/H ratio In hornblendes and a serpentine from St. Paul's Rocks, hydrogen isotope exchange, wlth little apparent oxygen isotope exchange, with ocean water IS suggested
238
Smaon M.F. SHEPPARD and Samuel EPSTEIN
Acknowledgements We are i n d e b t e d to the following persons for the generous d o n a t i o n o f sample material: R.E. Z a r t m a n , J F Levering, W.G. Melson and K.D. Watson. Discussions with J.F. Levering, H.P Taylor, T. S u z u o k l and R.E. Z a r t m a n have been beneficial. We are grateful to I. F r i e d m a n for his critical review o f this manuscript. This study was supported by National Science F o u n dation G r a n t No. G A 992 and by Project A g r e e m e n t No 7 u n d e r A t o m t c Energy Commlss~on C o n t r a c t No. A T (04-3)-767, CALT-767-58.
References [1] R N Clayton, I. Friedman, D L Graf, T K. Mayeda, W.F Meents and N.F. Shmap, The ongm of sahne formatlon waters" 1 Isotopic composition, J. Geophys Res. 71 (1966) 3869 [2] H. Craig, The isotopic geochemistry of water and carbon m geothermal areas, Conf. on Nuclear Geology m Geothermal Areas, Spoleto, Italy (1963) 17 [3] S M.F. Sheppard, R.L Nielsen and H.P. Taylor, Jr., Oxygen and hydrogen isotope ratios of clay minerals from porphyry copper deposits, Econ. Geol 64 (1969) 755. [4] R O Rye and J.R O'Nell, The OlScontent of water in primary fluid inclusions from Provldencm, north-cantral Mexico, Econ. Geol. 63 (1968) 232. [5 ] H P Taylor, J r , The oxygen isotope geochemistry of igneous rocks, Contrtb Mineral Petrol. 19 (1968) 1 [6] H P. Taylor, Jr and S Epstein, Hydrogen isotope evidence for influx of meteoric ground water rote shallow igneous mtruslves (abstract), Geol Soc Amer. Annual Meeting, Mexico City (1968) 294 [7] S.M.F. Sheppard and H.P. Taylor, Jr., Hydrogen and oxygen isotope evidence for the ongm of water in the Butte ore deposits and the Boulder bathohth, Montana, manuscript m preparatmn. [8] S Epstein and H.P Taylor, J r , Vanataon of O18/O 16 m minerals and rocks, in Researches in Geochemistry, ed. P.H. Abelson, vol. 2 (John Wiley, 1967) p 29. [9] H P Taylor, Jr. and S Epstein, Deutermm-hydrogen rataos m coexisting minerals of metamorphic and igneous rocks (abstract), Trans Am Geophys Union 47 (1966) 213 [ 10] H.P. Taylor, Jr., Stable Isotope studies of ultramaflc rocks and meteorites, in. Ultramaflc and Related Rocks, ed. P.J Wyllm (Wdey, New York, 1967) p 362 [11] N Kokubu, T Mayeda and H C. Urey, Deuterium content of minerals, rocks and hquld inclusion from reeks, Geochlm Cosmochlm Acta 21 (1961) 247.
[12] I. Friedman, Water and deutermm m pumice from the 1959-60 eruption of Kdauea volcano, Hawaii, U.S G.S, Prof. Paper 575B (1967) B 120. [13] T. Suzuokl and S Epstein, Hydrogen isotope fractlonatlon factors (~s) between muscowte, biotite, hornblende and water, Trans Amer Geophys. Umon 51 (1970) 451, and personal commumcatlon. [14] I. Friedman, Deutermm content of natural water and other substances, Geoctum Cosmochlm. Acta 4 (1953) 89 [15] J D Godfrey, The deutermm content of hydrous minerals from the east-central Sierra Nevada and Yosemite National Park, Geochim. Cosmochwn Acta 26 (1962) 1215. [16] H P Taylor, Jr., and S. Epstein, Relationship between O 18/O 16 raUos m coexlstmg mmerals of igneous and metamorphic rocks Part 1: Principle and experm~ental results, Geol. Soc Amer Bull. 73 (1962) 461. [17] R E Zartman, M R Brock, A.V Heyl and H H. Thomas, K-At and Rb-Sr ages of some alkalic mtruswe rocks from central and eastern United States, Amer Jour SoL 265 (1967) 848 [18] K.D. Watson, Kunberhte at Bachelor Lake, Quebec, Am Mineral 40 (1955) 565. [ 19] K D. Watson, Klmberhtes of eastern North America, m" Ultramaflc and Related Rocks, ed. P.J. Wylhe (John Wiley, 1967) p. 312. [20] J F Levering and J.R Rlchards, Potassmm-argon age study of possible lower-crust and upper-mantle inclusions m deep-seated intrusions, J Geophys Res 69 (1964) 4895 [21 ] J F Levering and J R. White, Granuhtlc and eclogat:c inclusions from basic pipes at Delegate, Australm, Contr Mineral. Petrol 21 (1969) 9. [22] A R Crawford, India, Ceylon and Pakistan" new age data and companson with Austraha, Nature 223 (1969) 380 [23] J F Lovenng, Personal communication (1968). [24] W G Melson, E Jarosewlch, V T. Bowen and G Thompson, St Peter and St Paul Rocks a hgh temperature, mantle derived intrusion, Science 155 (1967) 1532 [25 ] A F Wdhams, The genesis of dramond (Ernest Benn, London, 1932) [26] I. Kushtro, Y Syono and S. Aklmoto, Stability of phlogoplte at high pressures and possible presence of phlogopite m the earth's upper mantle, Earth Planet Sci Letters 3 (1967) 197. [27] I Kushlro and K. Aokl, Ongm of some ecloglte mcluslons m kmaberhte, Am Mineral. 53 (1968) 1347 [28] H P Taylor, Jr., J. Frechen and E.T Degens, Oxygen and carbon isotope studies of carbonatltes from the Laacher See District, West Germany and the Alno District, Sweden, Geochlm. Cosmochnn. Acta 31 (1967) 407. [29] D.G Brookms and K.D Watson, Carbonatlte associated with kimberhte froln Bachelor Lake, Quebec (abstract), Geol. See. Amer Annual Meeting, Mexico City (1968) 38
D/H AND 1~O/160 RATIOS [30] C.E Ttlley, The dumte-mylomtes of St Paul's Rocks (Atlantic), Am Jour Scl 245 (1947)483 [31] S Epstein, Oxygen and hydrogen isotope studies of serpentine In preparation Data reported by H P Taylor, J r , Stable isotope studies of ultramafic rocks and meteo-
239
rites, in Ultramafic and Related Rocks, ed P.J Wylhe (John Wiley, 1967) p 362 [32] B ~.rnason and T Slgurgelrsson, Deutermm content of water vapor and hydrogen m volcamc gas at Surtsey, Iceland, Geochlm Cosmochlm Acta 32 (1968) 807
I)~H A N D 1 8 0 / 1 6 0
RATIOS OF MINERALS OR LOWER CRUSTAL
OF POSSIBLE MANTLE
ORIGIN*
Simon M.F SHEPPARD** and Samuel EPSTEIN Dtvtslon of Geologtcal Sctences, Cahfornta Institute of Technology, Pasadena, California 91109 Received 3 June 1970 Revised version recewed 7 June 1970
D/H and 180/160 analyses are reported for 16 phlogopltes from 11 alkahc intrusions m the USA, Canada, South Africa, India and Austraha The D/H ratio of unaltered phlogoplte of possible mantle or lower crustal origin 1s-58 + 18 per rod, with no slgmficant vanatlon through space or time over the last 1140 my Phlogopltes and calcites from Bachelor Lake, Quebec, and hornblendes and a serpentine from St Paul's Rocks have undergone some isotopic exchange, possibly with ocean water at the latter locahty The D/H ratio m "juvende water" is estimated to be -48 + 20 per mfl
1. Introduction We have investigated the vanabihty of the D/H ratxo o f hydrous minerals o f possible mantle or lower crustal origin and attempt to set hm~ts on the D/H ratio o f "juvende water . . . . Juvenile water" refers here to that water which has never been part of the meteoric cycle. To determine the probable orxgm of volatfles m the earth's crust it ~s essentml that we can characterlze the various possible source materials. Recently the combined analyses for D/H and 180/160 m waters or hydrous minerals have been apphed with success to distinguish the connate, meteoric or primary magmatlc ongm o f a variety of crustal waters such as saline formation waters [ 1 ], geothermal waters [2], hydrothermal solutions [3,4] and the mflux o f meteoric waters into shallow igneous intrusions [ 5 - 7 ] . The 5180 content o f deep-seated water in lugh temperature isotopic equlhbrmm with slhcates ts basically that o f the rock. The composition o f this wa* Pubhcatlons of the Dlvaslon of Geological Sciences, Callforma Institute of Technology, Pasadena, Cahforma, Contrlbutaon No 1725. ** Now at Scottish Research Reactor Centre, East Kflbnde, Scotland.
ter is inferred to be 7 to 8 per mil [8] Since most rocks of deep-seated ongm c6ntam only a few per cent o f hydrogen, their D/H ratio is more diagnostic of "juvenile water". Thus hydrogen extracted from hydrous minerals o f such rocks is characteristic o f the OH or H 2 0 in the lower crust or upper mantle, and any interaction wlth meteoric ground waters should be lsotoplcally recogmzable The D/H ratio o f deepseated hydrogen is presently less satisfactorily defined because of b o t h the hmlted data available on statable samples [ 9 - 1 2 ] and incomplete experimental mineral-water fractlonatlon data [ 13 ]
2. Isotopic analyses and results Hydrogen and oxygen were quantitatively extracted after removal o f all absorbed water at temperatures o f 120 to 200°C from the pure mineral separates and the D/H and 180/160 ratios determined mass spectrometncally [ 1 4 - 1 6 ] Both D/H and 180/160 ratios are reported relatwe to standard mean ocean water (SMOW) m per mil umts. The overall analytical precision is + 0 . 1 - 0 . 2 per mil for 180/160, -+ 2 - 3 per mtl for D/H, and about + 0.05 per cent for H 2 0 content. Sixteen phlogopltes, occurring largely as fresh phe-
D/H AND tSO/t~O RATIOS
233
Table 1 Analytical results - phlogopltes. Sample No
Description
5D (%o)
51 a O ( %o )
Wt% H20
Age (my)
Ref.
Rose dome, Kansas 703B
Mica pendotlte
- 6 5 -+ 2 (2)
72
3 00
90*
[17]
- 5 0 - 3 (2) -63
6 0 +- 0 0 (2) 6.5
3 39 3.08
390**
[17]
- 5 6 + 4 (2)
6 0 + 0 2 (2)
2 97
267**
[17]
-60
7.3
4 96
269**
[17]
- 5 7 + 3 (3)
6 2 -+0 1 (2)
3.82
136"**
[17]
-75 + 1 (2)
6 9 +- 0 1 (2)
4.57
-48
68
4 44
146"**
[17]
- 43 + 3 (4) - 8 3 + 3 (2)
6 4 + 0.0 (2) 8 2 + 0.0 (2)
3.80 5 55
Klmberhte Klmberhte
-92 -92
7 9 + 0 0 (2) 5 9 + 0.1 (2)
3 69 3 64
1100"
[18,19]
Kmaberhte
- 7 0 + 2 (2)
66
3 37
1140"
[22,23]
-60
6.2 -+ 0 1 (2)
4.70
L. Cret
6 3 + 0.1 (2)
3 60
L. Cret
2 67
170"
Avon, Missouri 192B 194B
Ktmberhte Klmberhte
Roslclare, Ilhnols 189B
Kmabedlte
Elhott County, Kentucky 555B(b)
Klmberhte
Portland Pomt, New York 190B(c) 190B(d)
Klmberhte, xenocryst, excess Ar Fine-grained matrix with 190B(c)
Manhelm, New York 193B(a) 193B(b) 193B(c)
Klmberhte, xenocryst, excess Ar Fme-gramed matrix with 193B(a) and (b)
Bachelor Lake, Quebec P2zl P3 Panna, Indm GA 772
Phoenix Pipe, Kimberley, South Afnca K7
Kunberhte xenocryst
Dutoltspan Pipe, Ktmberley, South Africa Kma 8
Mica peridotlte xenocryst
- 5 3 + 4 (3)
Delegate, N S.W., Austraha GA 303
Basic pipe with Inclusions, excess At
-70
(8 8 + 0 3 (2)) 1
[20,21]
* K-Ar age only ** K-At and Rb-Sr ages concordant *** Rb-Sr age only, excess argon
1 There was sufficient coarse grained mica sample to do only a D/H analysis The taO/160 analyses were done on the associated finer grained mica. Our experience wtth the Manhetm sample suggests that the relationship between the D/H and 1aO/160 ratios of these two different separates may not be meaningful
Sunon M.F. SHEPPARD and Samuel EPSTEIN
234
Table 2 Analytacal results - hornblende, serpentine, calcite. Sample No.
Description
8D (%o)
61 s O (%0)
813 C (%0 PDB)
Ref.
St. Paul's Rocks SE-13 SE-13 SE-30 NE-4
Hornblende mylomte, whole rock Hornblende concentrate Hornblende mylomte, hornblende concentrate Serpentine from partially serpentmlzed perldotlte
-33
66
-36 - 4 0 +4 (2)
5 4 +0 3 (2) 5 4 +0.1 (2)
- 3 9 + 2 (2)
63
[24]
Bachelor Lake, Quebec l P2zl P3 P5d
Ktmberhte, calcite Klmberhte, calcite Ktmberhte, calcite
-6.1 -4 5 -5 6
9.5 10.1 104
[18,191
1 Twenty carbonates average STSr/a6Sr = 0 7040 + 0 0005, Sr = 3950 + 1500 ppm [29] nocrysts and xenocrysts, from 10 different alkahc Intrusions (klmberhtes and mica peridoutes) and one mafic breccia pipe were isotoplcally analyzed from locahtles m eastern and central North America, South Africa, Indm and Austraha, and two hornblendes and a serpentine from the St. Paul's Rocks All but the two South African phlogopltes were studied b y Zartman et al. [17] (eastern and central USA), Watson [18,19] (Quebec), Lovering and Rlchards [20], Lovermg and White [21] (Austraha), Crawford [22], Lovermg [23] (Indm) and Melson et al. [24] (St. Paul's Rocks), prowdmg data regarding their age, composition, petrography, etc The xsotop~c data, water content and summary descrlpt~ons are gwen m tables 1 and 2 Partml chemical analyses o f the two South African and Bachelor Lake, Quebec phlogopltes are given m table 3.
Our samples cover a variety of locations, range m age from Precambrlan (1140 my) to Cretaceous, have variations m K 2 0 and H 2 0 contents, and some contain excess argon Although there are b o t h natural and experimental data suggesting that primary phlogoplte Is or could be present m the upper mantle [ 2 5 - 2 7 ] , the depths o f crystalhzat~on o f our phlogopltes are unknown
3. Discussion
3 1. Phlogopttes The Isotopic data, tables 1 and 2, are compared m fig. 1 with sample location and age, and m fig. 2 with previous isotopic data for b~ot~tes from carbonatltes, other ultramafics, and plutonic granites and grano-
Table 3 Partial chemical analyses of phlogopltes (m weight per cent) *
K7 Kun 8 P2zl 190B(d)
Sample
K20
Phoemx, S Africa Dutoltspan, S Africa Bachelor Lake, Quebec Portland Point, New York
6.45 9 36 8 25 7.39**
* Analyst K Hoops using atomic absorption spectrophotometry ** Compare with 7 32 by Zartman et al. [17] *** Total tron as FeO
FeO** *
MgO
4 81 8.22 9 06 6.09
26 7 21 1 21 1 24.9
D/H AND lSO/160 RATIOS
-80
-400
ALKALIC INTRUSIONS Panna, India Bachelor Lake Avon
,age I (m;y.) 1"140 f fO0 390 269 Elliott Co Ros,clare =°67 Manhelm Y46 Portland Point ¢36 Rose Dome 90 L Cret S. Africa
I
I
-60 I
-40
I
I
The 180/160 ratios of the klmberlitic and pendotatm phlogopites are similar to values for whole rock ultramafic and mafic rocks (fig. 2) but tend to be slightly enriched in 180 by up to 1 to 2 per mfl relative to carbonatltlC micas [28] No simple correlation between 180/160 and D/H is observed. The water contents of most of our micas are very comparable to other igneous blotltes [e g 16,28] However, the xenocrysnc micas from Elhott County and the Phoenix pipe have OH-contents larger than the theoretical amount of OH in phlogoplte (4.3 wt per cent H 2 0 ) Both samples are associated with minor hydrous alteration products as detected by X-ray analyses, and have low K 2 0 contents (Elhott C o , 5 3 wt %, Phoenix, 6 5 w.t %) [table 2 in 17, table 3]. These data are not used to set limits on the D/H value of deep-seated water Excluding the Bachelor Lake (see below), EUlott Co. and Phoenix micas there is a tendency for the more D-rich xenocrysts to have a higher water content (fig 3) The four carbonatmc micas also show this tendency There is no relationship between K 2 0 and H 2 0 contents. Isotopic evidence for alteration possibly exists for the Bachelor Lake and the fine-grained matrix micas associated with the coarse xenocrystlc phlogopltes from Portland Point and Manhelm, New York Thus, our samples in general appear to be suitable for studylng "juvemle water" Considering the variety of field associations and tectonic environments represented by the alkahc, ul-
-20
I
I
I I I
H I I I
I
BASIC PIPE Delegate
170
I
ST. PAUL'S ROCKS ¢
SE-43 (hbl) S E - 3 0 (hbl) NE - 4 (serp)
¢
X I -400
I
I -80
I
I
I
I
-60
I
-40
-20
aD(%.) Fig. 1. Comparison of the D/H ratios of pheno- and xenocrystic phlogopltes from alkahc and basic intrusions with thetr locatmn and age. Included are data for hornblendes and serpentine from St Paul's Rocks dlontes. The range of the D/H ratios for pheno- and xenocrystlc phlogopltes is small, especially relative to that for hiotites from gramtlc intrusive rocks (fig 2) No age effect is observed. Five analyzed phlogopites from carbonatltes and a pyroxenlte [9] overlap the D-range observed here. 8D is independent of the excess argon content I
Maflc & Ultramaflc
I
I
235
I
I I I I: :l;,:::l:
BLft~
I
I
:
I-4-1
St Paul's Rocks Carbonahtes
II
Ultramaflcs [9,40]
II
.^,18. | v
,
l
to -455 I -400
I
iii w
I
I
I
II II .,
Maflcs [5AL42] Plutonm Gramtes & Granodmr#es [6,7,9A51
I
eL,,"m'H l~L
v
,
I I
I -80
I
I -60
8D (%.)
I
I -40
I 4
I 6
I
I 8
8 040 (%.)
Fig. 2 Comparison of the D/H and 180/160 ratios of minerals analyzed m this study wtth D/H data for phlogopltes or blotites from carbonatltes [9,28], ultramaflcs [9], plutomc gramtes and granodlontes [6,7,9,15], and for whole rock Hawaiian basalts [ll,12],and 18 O/ 'I-6 Odataforwholerocksfromultramaflcs[10],andmaflcs[5] Where a large number of 1 8 O/ 1 6 Odataare avalhble the isotopic range, mean and number of analyses are indicated BL = Bachelor Lake
236
Stmon M F SHEPPARD and Samuel EPSTEIN
iI
I I I I I I I 1
I I t I PHLOGOPITES
Manhelmo~
-. ~
004
4
"-:~ B a c h e l o r
~.~' L a k e
2 -t00
X
I
I -90
I
•
"-~ X ~*
I -80
X
I
I -70
I
-""*
"
Xo •
-
"'~ "-..
•
5~--
-
X Corbonahtes
""" Ec° P o r t l a n d ,.~ " - - . . . = Ph Point v~........ "-.
~
_
Ultramahcs 0 Matrix
•
-
•
I -60
with an Isotopic reservoir m which the xenocrysts were formed or possible exchange with local meteoric waters In either case xt ~s slgmficant that these relatwely large ~D differences are preserved in a single sample
-
f
I -50
f
I -40
~D (%0) Fig 3 Plot of 6D values for phlogopttes vs their water contents Data for the carbonatlt~c phlogopltes are taken from Taylor and Epstem [ 9 ] , and Taylor et al [28] Dashed hnes are drawn between coarse xenocrystlc phlogoplte and associated fine-grained matrix phlogoptte Ec = Elhott County, Ph = Phoemx pipe
tramafxc, carbonatltlc and basic micas, the range of 6D is quite restricted Although our rocks are not chemically representatwe of the mantle, we assume that our D/H ratios are broadly representatwe since isotopic fractlonatlons among different mineral phases are probably near zero at mantle temperatures However, small heterogeneltxes m D/H ratio could exist as a result of compositional variations m minerals and to the degassmghlstory Evaluation of the small varmtxons in both D/H and 180/160 of the micas must await further data
3 2. Matrtx phlogopttes The coarser grained xenocrystlc Manhelm and Portland Point phlogopltes are assocmted with finegrained matrix phlogopltes of either xenocrystlc or authlgemc ongm In bott. samples the water contents, D/H and 180/160 ratios of the matrix are &stmctly different from their assocmted coarser material (fig. 3), the 180/160 and water contents are higher and D/H ratxo Is lower Excess argon is not present in the matrix micas The ~sotoplc data indicate that the matrLX and associated coarse materxal were not formed under the same con&tlons The observed hydrogen and oxygen isotope differences are consistent with a lower temperature of exchange for the matrix mica
3.3. Bach elor Lake The Bachelor Lake phlogopltes are 20 per md or more lighter m D than any of our other samples and thus appear anomalous (fig. 2) Calcites coexisting with these phlogopltes (table 2) have 8180 values slgmficantly different from primary igneous carbonatlte values (6.0 to 8 5 per md) which represent high temperature equdlbratlon with slhcates [28] Such hydrogen and oxygen isotope compositions could result from the following (1) isotopic exchange with local ground waters, and (2) exchange with the hydrogen and oxygen containing reservoir to lower temperatures The slmdarltles between the 13C/12C ratios of the calcites and primary Igneous carbonatltlC calcites ( - 5 to - 8 per mtl,[28]) suggests that ff hydro° thermal exchange processes continued to submagrnao tic temperatures then the 13C/12C ratio of the exchange system was buffered by the calcites The carbon and oxygen isotope data dxscount weathering, or exchange with ground waters at earth-surface temperatures They do not necessardy exclude exchange at higher temperatures, m agreement with the low value for the 87Sr/86Sr ratio and the relatwely high Sr content of the calcites (table 2) [29]. All the isotopic data are consistent with late alteratlon, suggesting that exchange processes too&fled the once normal klmberhtlc or carbonatitlc isotopic ratios Therefore the D/H rattos of the Bachelor Lake m~cas are not used here to set ltmlts on mantle or lower crustal D/H values. 3.4. St Paul's R o c k The St. Paul's Rocks on the mid-Atlantic Ridge have been considered a htgh-temperature mantlederwed intrusion [24,30] Two hornblende concentrates and total rock were lsotoplcaUy analyzed from the brown alkah-nch hornblende mylomtes of the Southeast Islet (table 2) Smce hornblende is overwhelmlngly the dominant hydrous mineral present, the measured D/H ratios m these samples were not slgmficantly different The 180/160 ratios, which are more sensitive to the presence of Impurities, are
D/H AND 180/160 RATIOS different by about 1 per rml. We note that both primary and recrystallized hornblende, which could not be physically separated, coexist m each sample [24] The D/H ratios of the St. Paul's Rocks hornblendes are slightly enriched in deutermm relative to the igneous phlogopltes (fig. 2). The hydrogen isotope properties of biotite and hornblende are essentially similar as there IS no appreciable fractlonation of D between coexisting igneous biotite and hornblende [ 15]. The implied hydrogen ISOtope change could be lndicatwe of high-temperature exchange with a D-rich reservoir such as ocean water or possibly be a result of differences In chemistry of these amphiboles. These hornblendes have 180/160 ratios strndar to many other ultramafic and mafic hornblendes [5] The apparent lack of an accompanying oxygen ISOtope change could be a result of a very small ocean-water rock ratio so that the slhcate oxygen essentially controlled the 180/160 raho of the system Exchange may have occurred wlth recrystallizatlon during and after mylomtizatlon Chlorine-rich and hydrous phases are Important In the recrystallized assemblages [24] Further discussion must await the resolution of any ISOtopic differences between the primary and recrystallized hornblende The serpentine from the Northeast Islet is enriched in D relative to serpentmlte from the mld-Atlantlc Ridge and from the mohole test at Mayaguez, Puerto Rico [31 ] Exchange with oceanic water may be indicated. Thus, we exclude the D/H ratio of the St. Paul's Rocks hornblende as a candidate for the D/H ratio of "primary OH"
3 5. "Juventle water" We assign the D/H ratio of deep-seated phlogopltes, which have not undergone exchange at low temperatures, to be - 5 8 -+ 18 per mil. The isotopic composition of "juvenile water" depends upon the fractlonation factor between mica or amphibole and water PrehmInary experimentally determmed equilibrium ISOtOpic data by Suzuoki and Epstein [13] and an estimate by Sheppard et al [table 4 In 3] suggest that the hydrogen isotope fractIonatlon between phlogopite and water is on the order o f - 1 0 per mI1 at high temperatures (~ 700°C), indicating a 6D value of - 4 8 +- 20 per md In "]uvende water". We note that .~rnason and SlgurgeIrsson [32] mea-
237
sured 6D = - 5 5 3 -+ 0 5 per mil for the total hydrogen (water plus hydrogen gas) contained an the uncorttaminated volcanic gases over a 2.5 year period from Surtsey, Iceland These data combined with average 6D values for whole rock Hawanan basalts (-75%o) [11,12] set an approximate range of - 5 5 to - 7 5 per mll on the 6D value for total hydrogen in basalts. This range must be considered as very approximate since D/H ratios in Hawauan basalts are variable [ 12], and fractlonatlon of D caused by processes within the magma and associated,with the release of volatdes during eruption are lncomlSletely known. It is relevant to point out that If "juvenile water" in the lower crust or mantle is entirely in the form of "OH" then the isotopic composition could be that of OH reported here On the other hand, the attempt to define a ngld value for the D/H ratio of "juvenile water" may not be legitimate for two reasons (1) the very processes of degasslng of the earth's crust and mantle may affect an ISOtOpicchange m the "juvenile water", and (2) the D/H ratio of material refluxed back into the mantle from the crust may not be constant with either time or place It would be most Interesting to investigate a possible time effect on the D/H ratio of deep-seated water Our samples represent a rather narrow range In time (1140 my to present) We are cognizant of the prelmalnary nature of our assignment of the D/H values.
4. Conclusions 1 The D/H ratio of phlogoplte (or hornblende) of possible mantle or lower crustal origin is - 5 8 +- 18 per mll, with little variation through space or time over the last 1140 my. 2 The present estmaate for the D/H ratio in "juvende water" IS - 4 8 + 20 per mfl 3 Samples from Bachelor Lake, Quebec either have exchanged with local ground water or more probably have undergone oxygen and hydrogen isotope hydrothermal exchange processes without affecting the "primary" carbonatltlC value for 13C/12C ratio In the associated calcite. 4. To account for the higher D/H ratio In hornblendes and a serpentine from St. Paul's Rocks, hydrogen isotope exchange, wlth little apparent oxygen isotope exchange, with ocean water IS suggested
238
Smaon M.F. SHEPPARD and Samuel EPSTEIN
Acknowledgements We are i n d e b t e d to the following persons for the generous d o n a t i o n o f sample material: R.E. Z a r t m a n , J F Levering, W.G. Melson and K.D. Watson. Discussions with J.F. Levering, H.P Taylor, T. S u z u o k l and R.E. Z a r t m a n have been beneficial. We are grateful to I. F r i e d m a n for his critical review o f this manuscript. This study was supported by National Science F o u n dation G r a n t No. G A 992 and by Project A g r e e m e n t No 7 u n d e r A t o m t c Energy Commlss~on C o n t r a c t No. A T (04-3)-767, CALT-767-58.
References [1] R N Clayton, I. Friedman, D L Graf, T K. Mayeda, W.F Meents and N.F. Shmap, The ongm of sahne formatlon waters" 1 Isotopic composition, J. Geophys Res. 71 (1966) 3869 [2] H. Craig, The isotopic geochemistry of water and carbon m geothermal areas, Conf. on Nuclear Geology m Geothermal Areas, Spoleto, Italy (1963) 17 [3] S M.F. Sheppard, R.L Nielsen and H.P. Taylor, Jr., Oxygen and hydrogen isotope ratios of clay minerals from porphyry copper deposits, Econ. Geol 64 (1969) 755. [4] R O Rye and J.R O'Nell, The OlScontent of water in primary fluid inclusions from Provldencm, north-cantral Mexico, Econ. Geol. 63 (1968) 232. [5 ] H P Taylor, J r , The oxygen isotope geochemistry of igneous rocks, Contrtb Mineral Petrol. 19 (1968) 1 [6] H P. Taylor, Jr and S Epstein, Hydrogen isotope evidence for influx of meteoric ground water rote shallow igneous mtruslves (abstract), Geol Soc Amer. Annual Meeting, Mexico City (1968) 294 [7] S.M.F. Sheppard and H.P. Taylor, Jr., Hydrogen and oxygen isotope evidence for the ongm of water in the Butte ore deposits and the Boulder bathohth, Montana, manuscript m preparatmn. [8] S Epstein and H.P Taylor, J r , Vanataon of O18/O 16 m minerals and rocks, in Researches in Geochemistry, ed. P.H. Abelson, vol. 2 (John Wiley, 1967) p 29. [9] H P Taylor, Jr. and S Epstein, Deutermm-hydrogen rataos m coexisting minerals of metamorphic and igneous rocks (abstract), Trans Am Geophys Union 47 (1966) 213 [ 10] H.P. Taylor, Jr., Stable Isotope studies of ultramaflc rocks and meteorites, in. Ultramaflc and Related Rocks, ed. P.J Wyllm (Wdey, New York, 1967) p 362 [11] N Kokubu, T Mayeda and H C. Urey, Deuterium content of minerals, rocks and hquld inclusion from reeks, Geochlm Cosmochlm Acta 21 (1961) 247.
[12] I. Friedman, Water and deutermm m pumice from the 1959-60 eruption of Kdauea volcano, Hawaii, U.S G.S, Prof. Paper 575B (1967) B 120. [13] T. Suzuokl and S Epstein, Hydrogen isotope fractlonatlon factors (~s) between muscowte, biotite, hornblende and water, Trans Amer Geophys. Umon 51 (1970) 451, and personal commumcatlon. [14] I. Friedman, Deutermm content of natural water and other substances, Geoctum Cosmochlm. Acta 4 (1953) 89 [15] J D Godfrey, The deutermm content of hydrous minerals from the east-central Sierra Nevada and Yosemite National Park, Geochim. Cosmochwn Acta 26 (1962) 1215. [16] H P Taylor, Jr., and S. Epstein, Relationship between O 18/O 16 raUos m coexlstmg mmerals of igneous and metamorphic rocks Part 1: Principle and experm~ental results, Geol. Soc Amer Bull. 73 (1962) 461. [17] R E Zartman, M R Brock, A.V Heyl and H H. Thomas, K-At and Rb-Sr ages of some alkalic mtruswe rocks from central and eastern United States, Amer Jour SoL 265 (1967) 848 [18] K.D. Watson, Kunberhte at Bachelor Lake, Quebec, Am Mineral 40 (1955) 565. [ 19] K D. Watson, Klmberhtes of eastern North America, m" Ultramaflc and Related Rocks, ed. P.J. Wylhe (John Wiley, 1967) p. 312. [20] J F Levering and J.R Rlchards, Potassmm-argon age study of possible lower-crust and upper-mantle inclusions m deep-seated intrusions, J Geophys Res 69 (1964) 4895 [21 ] J F Levering and J R. White, Granuhtlc and eclogat:c inclusions from basic pipes at Delegate, Australm, Contr Mineral. Petrol 21 (1969) 9. [22] A R Crawford, India, Ceylon and Pakistan" new age data and companson with Austraha, Nature 223 (1969) 380 [23] J F Lovenng, Personal communication (1968). [24] W G Melson, E Jarosewlch, V T. Bowen and G Thompson, St Peter and St Paul Rocks a hgh temperature, mantle derived intrusion, Science 155 (1967) 1532 [25 ] A F Wdhams, The genesis of dramond (Ernest Benn, London, 1932) [26] I. Kushtro, Y Syono and S. Aklmoto, Stability of phlogoplte at high pressures and possible presence of phlogopite m the earth's upper mantle, Earth Planet Sci Letters 3 (1967) 197. [27] I Kushlro and K. Aokl, Ongm of some ecloglte mcluslons m kmaberhte, Am Mineral. 53 (1968) 1347 [28] H P Taylor, Jr., J. Frechen and E.T Degens, Oxygen and carbon isotope studies of carbonatltes from the Laacher See District, West Germany and the Alno District, Sweden, Geochlm. Cosmochnn. Acta 31 (1967) 407. [29] D.G Brookms and K.D Watson, Carbonatlte associated with kimberhte froln Bachelor Lake, Quebec (abstract), Geol. See. Amer Annual Meeting, Mexico City (1968) 38
D/H AND 1~O/160 RATIOS [30] C.E Ttlley, The dumte-mylomtes of St Paul's Rocks (Atlantic), Am Jour Scl 245 (1947)483 [31] S Epstein, Oxygen and hydrogen isotope studies of serpentine In preparation Data reported by H P Taylor, J r , Stable isotope studies of ultramafic rocks and meteo-
239
rites, in Ultramafic and Related Rocks, ed P.J Wylhe (John Wiley, 1967) p 362 [32] B ~.rnason and T Slgurgelrsson, Deutermm content of water vapor and hydrogen m volcamc gas at Surtsey, Iceland, Geochlm Cosmochlm Acta 32 (1968) 807